Multilayer reversal color material



y 1960 H. c. YUTZY ET AL 2,937,086

MULTILAYER REVERSAL COLOR MATERIAL Filed July 26, 1955 avuLs/cw LAYERS 54c cavm/M/va m1. LO/DAL SILVER A/VD o/ocm. HYOROOU/NO/VE /a- Jaws SENS/771E EMULSION colvm/lwlva raww 000mm x h RED SENSITIVE EMULSION 0/*, I CONMl/V/NG cm/v COUPLER suPPoRr J HENRY C. YUTZ) JOHN h. VAN CAMPEN INVENTORS nrmmygrs Unite tate Paten MULTILAYER REVERSAL COLOR MATERIAL Henry C. Yutzy and John H. Van Campen, Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Application July 26, 195s, Serial No. 524,362

2 Claims. (Cl. 96-74) This invention relates to photography and particularly to a multilayer. reversal color material.

a reversal color material in which difierently-sensitive silver halide emulsion layers containing both non-difiusing couplers capable of coupling with the oxidation product of primary aromatic amino developing agents and 2 [4"(3' tert. amylphenoxy benzamido) development nuclei, are separated from each other by 1 barrier layers. These barrier layers contain substances which check the difiusion of silver salts, such as colloidal silver, silver sulfide and fogged .silver halide emulsion.

The emulsion layers are exposed and developed in a black and white negative developer, then in a color developer of the p-phenylenediamine type containing a silver halide solvent. in the emulsion layers, and the barrier layers prevent The color developer forms positive dye images difiusion of the silver salts dissolved by the color developing solution, into neighboring emulsion layers.

The Meeussen and Bellay material has the disadvantage that the barrier layers increase the number of coatings and therefore increase thecost and complexity of the material.

Itis therefore an object of the present invention to provide an improved multilayer reversal color material. A further object is to provide a multilayer materialdeveloped by the solvent transfer process but not requiring barrier layers or interlayers.. Other objects will be apparent from the following description of our invention.

These objects are accomplished according to our invention by incorporating in the emulsion layers a non-diffusing coupler capable of reacting with the oxidation product of primary aromatic amino developing agents, a nucleating agent for precipitating dissolved silver salts, and a non-difliusing reducing agent or acceptor foroxi- "dized developer.

In the accompanying drawing the single figureis'a sectional view ofa sensitive material constructed according to our invention. 7 I

Our sensitive material preferablyhas three silver halide emulsions each sensitive to one ofjthe three primary -spectral-regions, although only. two sensitive layers may be employed. sensitive emulsion is preferably a fast gelatino-silver chlorobromide emulsion, andthe green-sensitive and redsensitive emulsions are preferably-slow, optically-sensitized gelatino-silver chlorobromide emulsions. Such If three s cnsitive layers are used, the bluecoatings require no filter for blue light, and may be I ice 2 U.S. Patent 2,600,788, and Weissberger U.S. Patent 2,298,443. Suitable couplers are, for example:

2 [a (4' tert. amylphenoxy) n butyrylaminolja 5- methyl-l-phenol benzamido)]-4-chloro-5-methyl-l-phenol 2 (2',4' di tert. amylphenoxyacetamino) 4,6 adie chloro-S-methylphenol 1 [p (p' tert.butylphenoxy) phenyl] 3 [a (ptert.butylphenoxy) propionylamino] -5 -pyrazolone 1(p [p' tert.butylphenoxy] phenyl) 3 (p- [or- {p' tert.butylphenoxy} propionylamino] benzoy1- amino-S-pyrazolone) 1 (2',4',6 trichlorophenyl) 3 [3" (2"',4" ditert.amylphenoxyacetamido) -b enz amido] -5-pyrazolone Meeussen and Bellay US. Patent 2,673,800 describes N (4 benzoylacetaminobenzenesulfonyl) N (7 pb enylpropyl -p-toluidine N (p benzoylacetaminobenzenesnlphonyl) N phenylpropyl)-p-tert.-amylaniline I N (p benzoylacetaminobenzenesulphonyl) N benzylm-toluidine 1 If faster negative-type emulsions are used, a blue light absorber between the blue-sensitive emulsion and, the greenand red-sensitive emulsions would be necessary. Colloidal silver cannot be used for this purpose, but'a yellow dye filter layer such as described in Saunders et a1. U.S. application Serial No. 476,066 would be suitable.

The nueleating agent for dissolved silver salts, which nucleating agent is incorporated in-the emulsion layer, comprises colloidal metals, e.g., silver, metallic sulfides, e.g., silver sulfide, colloidal sulfur, or'fogged silver halide. The acceptor for oxidized developer is a non-difiusing reducing agent such as amyl hydroquinone, lauryl hydroquinone, 2,5-di-sec. o-ctyl 'hydroquinone, 2,5-didodecyl v hydroquinone, dodecyl catechol, 2,5-di-n-octyl hydro quinone, 2,6-di-n-octyl hydroquinone, and others.

The following example illustrates our invention:

Red-sensitive l'ayer The following were mixed and coated over 2160 square feet of cellulose ester film support: 1 i

One mole of red-sensitive gelatino-silver chlorobromide emulsion containing grams of gelaf Water to grams Green-sensitive laye r The following were mixed and coated over the redsensitive emulsion covering an areaof 2160 square feet:

One mole of green-sensitive gelatino-silver chlorobromide emulsion containing 80 grams of gelatin (80% chloride) grams 10% gelatin solution do 8160 Colloidal silver dispersion (as above) do 1160 Magenta coupler dispersion do 1545 2,5-di-sec. octyl hydroquinone dispersion do 618 Saponin 7.5% solution cc 820 Mucochloric acid 2.64% solution cc 214 Water to grams 24,500

Blue-sensitive layer The following were mixed and coated over the greensensitive emulsion covering an area of 1440 square feet:

Onemole of high speed gelatino-silver chlorobromide emulsion containing 80 grams gel The above dispersions were prepared as follows:

2,5-di-sec. octyl hydroquinone dispersion 3.5 grams of the di-octyl hydroquinone were dissolved in 105 cc. of dibutylphthalate and the solution dispersed in a mixture of 250 grams of 10% gelatin solution and 50 cc. of Alkanol B solution. The dispersion was run through a colloid mill and brought to a final weight of 500 grams by adding water.

Coupler dispersions The coupler dispersions were prepared by dispersing a solution composed of 56 grams of coupler and 128 cc. of dibutylphthalate in a mixture of 260 grams of gelatin solution and 50 cc. of 5% Alkanol B solution. This dispersion was run through a colloid mill several times and finally adjusted to a total weight of 500 grams by adding water.

The cyan coupler was Z-(diamylphenoxy acetamino)- 4,6-dichloro-5-methyl phenol. The magenta coupler was 1-(2,4,6-trichlorophenyl)-3-[3'-(2",4"-di-tert. amylphenoxy acetamido)-benzamido]-5-pyrazolone. The yellow coupler was N-(4-benzoylacet-aminobenzene sulfonyl)- N-(y-phenyl propyl)-p-toluidine.

Exposed strips of this three-layer coating were processed as follows:

Film was developed'for 5 to 10 minutes at 68 F. in

a developer of the following composition:

Grams N-methyl-p aminophenol sulfate 6 Hydroquinone 10 Sodium sulfite 50 Sodium carbonate 30 Potassium bromide 5 Water to 1 liter.

After a short acetic acid stop bath and water wash the film was then developed in a color developer of the following composition:

Water to 1 liter.

After an acetic acid stop bath and water wash the film was then treated in the usual ferricyanide and bromide bleach bath, washed, fixed with hypo and washed. These '4 processed strips showed excellent reversal, low stain and good color separation.

In place of potassium thiocyanate other silver halide solvents such as hypo, ammonium sulfite, etc. can be used in the color development.

In the accompanying drawing which shows a sectional view of a film coated according to our invention, 10 is a support of film base, glass, synthetic resin or other suitable material on which is coated the successive emulsion layers 11, 12 and 13, sensitive respectively to red, green and blue light and containing the appropriate color coupler as described above, a nucleating agent such as col loidal silver and a non-diffusing reducing agent or acceptor for oxidized developer.

It will be understood that various changes may be made in the process and materials described above and that our invention is to be construed as limited only by the scope of the appended claims.

What we claim is:

1. A multilayer reversal color material comprising a support having thereon a red-sensitive gelatino-silver halide emulsion layer containing a non-diffusing cyan color-forming compound, a green-sensitive gelatino-silver halide emulsion layer containing a magenta color-forming compound, and a blue-sensitive gelatino-silver halide emulsion layer containing a yellow color-forming compound, said emulsion layers being immediately superposed on each other and said color-forming compounds being capable of coupling with the oxidation product of a primary aromatic amino color developer, each of said emulsion layers containing a nucleating agent selected from the class consisting of collodial silver, silver sulfide, collodial sulfur, and fogged silver halide for catalyzing the precipitation of dissolved silver salts and a nondiflusing reducing agent for oxidized developer, said nondifiusing reducing agent being selected from the class consisting of higher alkyl hydroquinones containing at least 5 carbon atoms in the alkyl radical and higher alkyl catechols containing at least 5 carbon atoms in the alkyl radical.

2. A multilayer reversal color material comprising a support having thereon a red-sensitive gelatino-silver halide emulsion layer containing a non-diffusing cyan color-forming compound, a green-sensitive gelatino-silver halide emulsion layer containing a magenta color-forming compound, and a blue-sensitive gelatino-silver halide emulsion layer containing a yellow color-forming compound, said emulsion layers being immediately superposed on each other and said color-forming compounds being capable of coupling with the oxidation product of a primary aromatic amino color developer, each of said emulsion layers containing colloidal silver and 2,5-di-sec.' octyl hydroquinone.

References Cited in the file of this patent UNITED STATES PATENTS 2,306,410 Schinzel Dec. 29, 1942 2,403,721 Jelley et al. July 9, 1946 2,673,800 Meeussen et al Mar. 30, 1954 2,712,995 Weyde July 12, 1955 2,725,298 Yutzy et a1 Nov. -29, 1955 2,740,717 Yutzy et a1. Apr. 3, 1956 OTHER REFERENCES Mees: The Theory of the Photographic Practice, pages 87-88, The MacMillan Co., New York, 1954. 

1. A MULTILAYER REVERSAL COLOR MATERIAL COMPRISING A SUPPORT HAVING THEREON A RED-SENSITIVE GELATINO-SILVER HALIDE EMULSION LAYER CONTAINING A NON-DIFFUSING CYAN COLOR-FORMING COMPOUND, A GREEN-SENSITIVE GELATINO-SILVER HALIDE-EMULSION LAYER CONTAINING A MAGENTA COLOR-FORMING COMPOUND, AND A BLUE-SENSITIVE GELATINO-SILVER HALIDE EMULSION LAYER CONTAINING A YELLOW COLOR-FORMING COMPOUND, SAID EMULSION LAYERS BEING IMMEDIATELY SUPERPOSED ON EACH OTHER AND SAID COLOR-FORMING COMPOUNDS BEING CAPABLE OF COUPLING WITH THE OXIDATION PRODUCT OF A PRIMARY AROMATIC AMINO COLOR DEVELOPER, EACH OF SAID EMULSION LAYER CONTAINING A NUCLEATING AGENT SELECTED FROM THE CLASS CONSISTING OF COLLODIAL SILVER, SILVER SULFIDE, COLLODIAL SULFUR, AND FGGED SILVER HALIDE FOR CAATALYZING THE PRECIPITATION OF DISSOLVED SILVER SALTS AND A NONDIFFUSING REDUCING AGENT FOR OXIDIZED DEVELOPER, SAID NONDIFFUSING REDUCING AGENT BEING SELECTED FROM THE CLASS CONSISTING OF HAGHER ALKYL HYDROQUINONES CONTAINING AT LEAST 5 CATRBON ATOMS IN THE ALKYL RADICAL AND HIGHER ALKYL CATECHOLS CONTAINING AT LEAST 5 CARBON ATOMS IN THE ALKYL RADICAL. 